CN109928425A - A method of it reducing metatitanic acid and is converted into rutile titanium dioxide calcination temperature - Google Patents
A method of it reducing metatitanic acid and is converted into rutile titanium dioxide calcination temperature Download PDFInfo
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- CN109928425A CN109928425A CN201910330072.5A CN201910330072A CN109928425A CN 109928425 A CN109928425 A CN 109928425A CN 201910330072 A CN201910330072 A CN 201910330072A CN 109928425 A CN109928425 A CN 109928425A
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Abstract
The invention discloses a kind of methods that reduction metatitanic acid is converted into rutile titanium dioxide calcination temperature to be calcined at 800 ± 20 DEG C in carbon containing, hydrogen, oxygen at least two or more zinc compound and ammonium salt Combined Treatment agent, be obtained rutile titanium dioxide.The rutile phase titanium dioxide particles prepared through this method are uniform in size, particle diameter distribution is small, and method preparation does not change original production technology, reduce calcination temperature, and operation is easy, and easy to industrialized production, low energy consumption, and economic benefit and social benefit are preferable.
Description
Technical field
The invention belongs to pigment preparation technical fields, are related to the method for titanium dioxide preparation, in particular to a kind of to reduce inclined titanium
The method that acid is converted into rutile titanium dioxide calcination temperature.
Background technique
In general, in sulfuric acid process, metatitanic acid crystallinity made from titanium hydrolysis is bad (brilliant using rutile-type
Except kind), it is necessary to being calcined for a long time at a high temperature of 1050 DEG C or so can just make product be completely converted into rutile crystal type.But
That metatitanic acid crystalline solid crystal in prolonged pyroprocess can generate serious sintering, and there are many lattice defect, crystal grain it is excessive and
Hardness is high, and product pigment performance is very poor；In addition, high temperature can also cause lattice deoxidation, making product is in grey phase, and it is white to directly affect product
Degree.Therefore, the promotor and crystal structure adjusting agent that must add some rutilizations in metatitanic acid in production, make Ti02To close
The speed of reason is grown up, produced under lower calcination temperature transformation of crystal completely, be of moderate size, the pigment grain of neat appearance
Son.
It is lured the study found that some metal oxides all have in the anatase titanium dioxide of titanium dioxide into rutile-type conversion process
It leads, promote and the effect of positive catalyst, it is considered that cationic ionic radius is smaller, and the effect of rutilization is promoted to get over
By force, in TiO2Some compounds are added during crystal transfer, such as: Cl-、ZnO、MgO、Al2O3、V2O5、SnO2Deng gold can be promoted
The generation of red stone-type object phase reduces crystal transfer temperature, shortens the crystal transfer time.Document report, industrial common promotion
Agent has the oxide and salt and TiO 2 sol of the elements such as zinc, magnesium, antimony, tin, aluminium.Such as: Guo Junhuai (rutile-type
TiO2Quick crystal transfer, applied chemistry, 2003,20 (7): 647-650), titanium liquid carry out ordinary-pressure hydrolysis when, be added SnCl2
With compound crystal seed made of titanium salt, the SnO that mass fraction is 70% is introduced2As crystal transfer promotor, can effectively make sharp
Titanium ore type TiO2It is changed into rutile-type, TiO2Crystal transfer temperature be reduced to 870 DEG C, and greatly shorten and complete crystal transfer
Required time avoids material from being sintered, and is of moderate size, neat appearance, the good rutile TiO of optical property2.Research is also
It was found that the Zn that mass fraction is 0.5% is added in salt treatment2+, further speeded up crystal transfer process.(the golden red such as Zhao Yan
The preparation and application of calcining seeds in stone-type production process of titanium pigment, process engineering journal, 2009,9 (4): 750-753), it will be certainly
Combinations kind is used for the salt treatment of metatitanic acid, when Seed charge 3%, 5%, 900 DEG C of calcination temperature, calcination time 2h, TiO2
Rutile crystal type conversion ratio up to 99% or more.The method of CN1242923C is: will be added with rutile calcining seeds and through rinsing
Qualified metatitanic acid cake spends ion water making and starches at metatitanic acid, is then added by potassium compound, phosphorus compound and aluminium compound
The salt treatment agent of crystalline controlling agent composition, then the temperature lower calcination conversion by the metatitanic acid after salt treatment at 800-1050 DEG C,
Rutile type titanium white first product is made.But the analysis testing result such as do not provide XRD.The method of CN104817105B is: making
Carrying out salt treatment with high zinc salt accelerates rutile crystal type to convert, raising conversion ratio, and 925-980 DEG C of calcination temperature.
In terms of document and patent report, it is converted into rutile titanium dioxide technique in the metatitanic acid of sulfuric acid process preparation,
The inorganic salts such as zinc salt, aluminium salt, phosphate are added as salt treatment agent, and most of calcination temperature is at 870 DEG C or more.Due to through height
The rutile titanium dioxide pigment performance that temperature calcining obtains is undesirable, and partial size is coarse, and hardness is high, and whiteness is not good enough.In order to reduce
Calcination temperature improves the pigment performance of rutile-type, and this patent is by being converted into rutile titanium dioxide to anatase titanium dioxide metatitanic acid
Principle analyzed, using in carbon containing, hydrogen, oxygen at least two or more zinc compound-inorganic ammonium salt as salt treatment agent, reduce
Calcination temperature achievees the purpose that reduce energy consumption and improves pigment product performance.
Summary of the invention
The purpose of the invention is to overcome current sulfuric acid process rutile titanium dioxide preparation process calcination temperature
Excessively high, the deficiencies of influencing its pigment performance, is provided and a kind of is made in carbon containing, hydrogen, oxygen at least two or more zinc compound-ammonium salt
To combine salt treatment agent, the method for preparing rutile titanium dioxide.
The technical solution of the present invention is as follows:
A method of it reducing metatitanic acid and is converted into rutile titanium dioxide calcination temperature, it will be through bleaching and washing process
Metatitanic acid be added to the water, add zinc compound-ammonium salt composite treating agent, stir it is lower carry out salt treatment, then filtering is drained,
Calcining crushes, obtains rutile titanium dioxide.
The raw material components and mass fraction that above-described salt treatment is selected are as follows: 100 parts of metatitanic acid, zinc compound 0.1-2
Part, 0.1-3 parts of ammonium salt, 100-500 parts of water.
Above-described zinc compound is mainly to have carbon containing the zinc compound in carbon, hydrogen, oxygen more than at least two elements
Sour zinc, basic zinc carbonate, zinc oxalate, zinc formate, zinc acetate, zinc hydroxide, zinc gluconate, zinc citrate.
Ammonium salts mentioned above is carbon containing ammonium salt, is mainly had: ammonium carbonate, ammonium hydrogen carbonate, ammonium acetate, ammonium formate, oxalic acid
Ammonium, ammonium citrate.
The mass ratio 1:1-5 of the above metatitanic acid and water.
Above-described zinc compound additional amount is the 0.1-2% of metatitanic acid, and ammonium salts mentioned above additional amount is inclined titanium
The 0.1-3% of acid.
The 1-5% that total weight is metatitanic acid is added in above-described composite treating agent.
The condition of above-described salt treatment is: temperature is room temperature, and mixing speed 250r/min, the processing time is 0.5-
1 hour.
The temperature of above-described calcining is 800 ± 20 DEG C, and above-described calcination time is 2-5 hours.
The advantages and positive effects of the present invention:
1, a kind of reduction metatitanic acid of the invention is converted into the salt processing method of rutile titanium dioxide calcination temperature, leads to
The type for changing salt treatment agent is crossed, calcination temperature is reduced, compared with other salt treatment agents, raw material is easy to get inexpensive, is conducive to drop
Low energy consumption.
2, a kind of salt treatment side for reducing metatitanic acid and being converted into rutile titanium dioxide calcination temperature provided by the invention
Method, used ammonium salt is volatile, and additional amount is few, calcines through 800 ± 20 DEG C, and noresidue does not influence the usability of titanium dioxide
Energy.
3, a kind of reduction metatitanic acid of the invention is converted into the salt processing method of rutile titanium dioxide calcination temperature, nothing
The production procedure that original rutile titanium dioxide need to be changed makes the technology with more exploitativeness, and operation is easy, and is easy to work
Industry metaplasia produces, and lower production costs, economic benefit and social benefit are preferable.
Detailed description of the invention
Fig. 1: being the XRD diagram for the titanyl hydroxide starting material that this case uses, a-JCPDS:21-1272, B- metatitanic acid, with PDF card
Number 21-1272 is consistent.
Fig. 2: be embodiment 1 prepare titanium dioxide and external product XRD comparison XRD diagram, a-JCPDS:21-1276,
1 product of b- external product XRD, c- embodiment, it can be seen that this method prepares product and certain external rutile titanium dioxide one
It causes, it is consistent with card number PDF21-1276 rutile titanium dioxide.
Fig. 3: being the grain size distribution of titanium dioxide prepared by embodiment 1, and this method prepares product average grain diameter and is
149.3nm, particle size range is between 129.27-169.33nm, narrowly distributing.
Fig. 4: being the SEM figure of titanium dioxide prepared by embodiment 1, from picture, it can be seen that, this method prepares product grain
Edge clear illustrates that good crystallinity, granular size are more uniform.
Fig. 5: being this case salt treatment process flow chart.
Specific embodiment
Below in conjunction with drawings and examples, the invention will be further described, the description of embodiment only this hair for ease of understanding
It is bright, rather than to the limitation that the present invention protects.
One, embodiment is prepared
Embodiment 1
1, a kind of method for reducing metatitanic acid and being converted into rutile titanium dioxide calcination temperature, selects raw material components and matter
Amount are as follows: metatitanic acid 100Kg, zinc carbonate 0.2Kg, ammonium carbonate 3Kg, water 200Kg.
2, preparation method:
200Kg water is added in beaker in the 100Kg metatitanic acid for bleaching and the washing process of learning from else's experience, and 0.2Kg carbon is added after stirring
Sour zinc and 1Kg ammonium carbonate stir 30 minutes at room temperature, and filtering is drained according to a conventional method, is calcined at 780 DEG C, and crushing obtains gold
Red stone-type titanium dioxide, conversion ratio 98.77%.
Embodiment 2
1, a kind of method for reducing metatitanic acid and being converted into rutile titanium dioxide calcination temperature, selects raw material components and matter
Amount are as follows: metatitanic acid 100Kg, zinc acetate 1Kg, ammonium acetate 0.5Kg, water 300Kg.
2, preparation method:
300Kg water is added in beaker in the 100Kg metatitanic acid for bleaching and the washing process of learning from else's experience, and 1Kg acetic acid is added after stirring
Zinc and 0.5Kg ammonium acetate stir 40 minutes at room temperature, and filtering is drained according to a conventional method, is calcined at 810 DEG C, and crushing obtains gold
Red stone-type titanium dioxide, conversion ratio 99.45%.
Embodiment 3
1, a kind of method for reducing metatitanic acid and being converted into rutile titanium dioxide calcination temperature, selects raw material components and matter
Measure number are as follows: metatitanic acid 100Kg, oxalic acid zinc compound 0.5Kg, ammonium hydrogen carbonate 1.5Kg, water 400Kg.
2, preparation method:
400Kg water is added in beaker in the 100Kg metatitanic acid for bleaching and the washing process of learning from else's experience, and 0.5Kg grass is added after stirring
Sour zinc and 1.5Kg ammonium hydrogen carbonate stir 45 minutes at room temperature, and filtering is drained according to a conventional method, is calcined, is crushed at 800 DEG C
To rutile titanium dioxide, conversion ratio 99.69%.
Embodiment 4
1, a kind of method for reducing metatitanic acid and being converted into rutile titanium dioxide calcination temperature, selects raw material components and matter
Measure number are as follows: metatitanic acid 100Kg, zinc hydroxide 1Kg, ammonium formate 1Kg, water 100-500Kg.
2, preparation method:
300Kg water is added in beaker in the 100Kg metatitanic acid for bleaching and the washing process of learning from else's experience, and 1Kg hydrogen-oxygen is added after stirring
Change zinc and 1Kg ammonium formate, at room temperature, stirs 30 minutes, filtering is drained according to a conventional method, is calcined at 820 DEG C, and crushing obtains gold
Red stone-type titanium dioxide, conversion ratio 99.21%.
Embodiment 5
1, a kind of method for reducing metatitanic acid and being converted into rutile titanium dioxide calcination temperature, selects raw material components and matter
Measure number are as follows: metatitanic acid 100Kg, zinc gluconate 2Kg, ammonium oxalate 0.7Kg, water 150Kg.
2, preparation method:
150Kg water is added in beaker in the 100Kg metatitanic acid for bleaching and the washing process of learning from else's experience, and 2Kg grape is added after stirring
Saccharic acid zinc and 0.7Kg ammonium oxalate stir 40 minutes at room temperature, and filtering is drained according to a conventional method, is calcined, is crushed at 780 DEG C
To rutile titanium dioxide, conversion ratio 98.91%.
Embodiment 6
1, a kind of method for reducing metatitanic acid and being converted into rutile titanium dioxide calcination temperature, selects raw material components and matter
Measure number are as follows: metatitanic acid 100Kg, zinc formate 3Kg, ammonium citrate 0.5Kg, water 300Kg.
2, preparation method:
300Kg water is added in beaker in the 100Kg metatitanic acid for bleaching and the washing process of learning from else's experience, and 3Kg formic acid is added after stirring
Zinc and 0.5Kg ammonium citrate stir 50 minutes at room temperature, and filtering is drained according to a conventional method, is calcined at 800 DEG C, and crushing obtains
Rutile titanium dioxide, conversion ratio 98.72%.
Claims (7)
1. a kind of method for reducing metatitanic acid and being converted into rutile titanium dioxide calcination temperature, which is characterized in that will be through bleaching
It is added to the water with the metatitanic acid of washing process, adds zinc compound-ammonium salt composite treating agent, stirs lower progress salt treatment, so
Filtering is drained afterwards, is calcined, and is crushed, is obtained rutile titanium dioxide；
The raw material components and mass fraction that the salt treatment is selected are as follows: 100 parts of metatitanic acid, 0.1-2 parts of zinc compound, ammonium salt
0.1-3 parts, 100-500 parts of water；
The zinc compound is mainly to have zinc carbonate, alkali containing the zinc compound in carbon, hydrogen, oxygen more than at least two elements
Formula zinc carbonate, zinc oxalate, zinc formate, zinc acetate, zinc hydroxide, zinc gluconate, zinc citrate；
The ammonium salt is carbon containing ammonium salt, is mainly had: ammonium carbonate, ammonium hydrogen carbonate, ammonium acetate, ammonium formate, ammonium oxalate, citric acid
Ammonium；
The mass ratio 1:1-5 of the metatitanic acid and water.
2. a kind of method for reducing metatitanic acid and being converted into rutile titanium dioxide calcination temperature according to claim 1,
It is characterized in that, the zinc compound additional amount is the 0.1-2% of metatitanic acid.
3. a kind of method for reducing metatitanic acid and being converted into rutile titanium dioxide calcination temperature according to claim 1,
It is characterized in that, the ammonium salt additional amount is the 0.1-3% of metatitanic acid.
4. a kind of method for reducing metatitanic acid and being converted into rutile titanium dioxide calcination temperature according to claim 1,
It is characterized in that, the 1-5% that total weight is metatitanic acid is added in the composite treating agent.
5. a kind of method for reducing metatitanic acid and being converted into rutile titanium dioxide calcination temperature according to claim 1,
It is characterized in that, the condition of the salt treatment is: temperature is room temperature, and mixing speed 250r/min, the processing time is 0.5-1
Hour.
6. a kind of method for reducing metatitanic acid and being converted into rutile titanium dioxide calcination temperature according to claim 1,
It is characterized in that, the temperature of the calcining is 800 ± 20 DEG C, above-described calcination time is 2-5 hours.
7. a kind of method for reducing metatitanic acid and being converted into rutile titanium dioxide calcination temperature according to claim 1,
It is characterized in that, selecting raw material components and mass number are as follows: metatitanic acid 100Kg, oxalic acid zinc compound 0.5Kg, ammonium hydrogen carbonate
1.5Kg, water 400Kg；
Preparation method:
400Kg water is added in beaker in the 100Kg metatitanic acid for bleaching and the washing process of learning from else's experience, and 0.5Kg zinc oxalate is added after stirring
It is stirred 45 minutes at room temperature with 1.5Kg ammonium hydrogen carbonate, filtering is drained according to a conventional method, is calcined at 800 DEG C, and crushing obtains gold
Red stone-type titanium dioxide, conversion ratio 99.69%.
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2019
- 2019-04-23 CN CN201910330072.5A patent/CN109928425B/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55158129A (en) * | 1979-05-14 | 1980-12-09 | Lion Corp | Manufacture of high-whiteness titanium dioxide pigment |
| CN1007970B (en) * | 1986-09-10 | 1990-05-16 | 南开大学 | Manufacturing method for rulite titanium dioxide |
| CN1101625A (en) * | 1993-10-09 | 1995-04-19 | 宁甲保 | Method for preparing titanium dioxide from titanium-riched material |
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| CN101062780A (en) * | 2006-04-26 | 2007-10-31 | 四川大学 | Nano titanium oxide and mechanical force chemical reaction preparation method for its composite powder |
| CN101844803A (en) * | 2009-03-27 | 2010-09-29 | 比亚迪股份有限公司 | Rutile type titanium dioxide and preparation method thereof |
| CN102765751A (en) * | 2012-07-13 | 2012-11-07 | 重庆普源化工工业有限公司 | Preparation method of nanometer titanium dioxide |
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| CN104667901A (en) * | 2013-11-29 | 2015-06-03 | 中国科学院兰州化学物理研究所 | Preparation method for denitration catalyst carrier nano titanium dioxide |
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